A Versatile Cu Metal-Organic Framework Exhibiting High Gas Storage Capacity with Selectivity for CO : Conversion of CO to Cyclic Carbonate and Other Catalytic Abilities.

A linear tetracarboxylic acid ligand, H L, with a pendent amine moiety solvothermally forms two isostructural metal-organic frameworks (MOFs) L (M=Zn , Cu ). Framework L can also be obtained from L by post- synthetic metathesis without losing crystallinity. Compared with L , the L framework exhibits high thermal stability and allows removal of guest solvent and metal-bound water molecules to afford the highly porous, L '. At 77 K, L ' absorbs 2.57 wt % of H at 1 bar, which increases significantly to 4.67 wt % at 36 bar. The framework absorbs substantially high amounts of methane (238.38 cm  g , 17.03 wt %) at 303 K and 60 bar. The CH absorption at 303 K gives a total volumetric capacity of 166 cm  (STP) cm at 35 bar (223.25 cm  g , 15.95 wt %). Interestingly, the NH groups in the linker, which decorate the channel surface, allow a remarkable 39.0 wt % of CO to be absorbed at 1 bar and 273 K, which comes within the dominion of the most famous MOFs for CO absorption. Also, L ' shows pronounced selectivity for CO absorption over CH , N , and H at 273 K. The absorbed CO can be converted to value-added cyclic carbonates under relatively mild reaction conditions (20 bar, 120 °C). Finally, L ' is found to be an excellent heterogeneous catalyst in regioselective 1,3-dipolar cycloaddition reactions ("click" reactions) and provides an efficient, economic route for the one-pot synthesis of structurally divergent propargylamines through three-component coupling of alkynes, amines, and aldehydes.